CD
O
Report No. 78-OCM-4
AIR POLLUTION
EMISSION TEST
DENKA CHEMICAL CORPORATION
HOUSTON, TEXAS
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Air Quality Planning and Standards
Emission Measurement Branch
Research Triangle Park. North Carolina
-------
DATE:
SUBJECT:
FROM:
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Air Quality Planning and Standards
8/14/78 Research Triangle Park, North Carolina 27711
Source Test Report
J. E. McCarley, Chief, Field Testing Section,
Emission Measurement Branch, ESED (MD-13)
TO: See Below
The enclosed final source test report is submitted for your
information. Any questions regarding the test should be directed
to the Project Officer (telephone: 8/629-5243). Additional
copies of this report are available from the ERC Library, Research
Triangle Park, North Carolina 27711.
Industry: Maleic Anhydride Manufacturing
Process: Partial oxidation .of benzene
Company: Denka Chemical Corp.
Location: Houston, Texas
Project Report Number: 78-OCM-4
Project Officer: Dennis Holzschuh
Enclosure
Addressees:
John Nader, ESRL (MD-46)
flrch MacQueen, MDAD (MD-14)
John Clements, EMSL (MD-77)
Frank Biros, ESSE (MD-EN-341)
Director, Air & Hazardous Materials Division, Region
(copy enclosed for State agency)
APTIC (MD-18)
VI
F. PA FOF'M 1320-6 (REV. 3-7&i
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STATIONARY SOURCE TESTING OF A MALEIC ANHYDRIDE PLANT AT THE
DENKA CHEMICAL CORPORATION, HOUSTON, TEXAS
by
William H. Maxwell
George W. Scheil
FINAL REPORT
EPA Contract No. 68-02-2814, Work Assignment No. 5
EPA Project No. 78-OCM-4
MR! Project No. 4468-L(5)
For
Emission Measurement Branch
Field Testing Section
Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Attn: Mr. J. E. McCarley, Jr.
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PREFACE
The work reported herein was conducted by Midwest Research Institute
under Environmental Protection Agency Contract No. 68-02-2814, Work Assign-
ment No. 5, and Change No. 1.
The project was under the supervision of Mr. Doug Fiscus, Head, Field
Programs Section, and Mr. William Maxwell, Program Manager. Mr. Maxwell
served as field team leader and was assisted in the field by Messers George
Scheil, John LaShelle, Chris Cole, and in the lab by Messers George Cobb and
Doug Bischoff.
Approved for:
MIDWEST RESEARCH INSTITUTE
J. Shannon, Director
\J Environmental and Materials
Sciences Division
iii
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CONTENTS
Preface iii
Tables and Figures vi
1. Introduction 1
2. Summary and Discussion of Results 2
3. Process Description and Operation 10
4. Location of Sample Points 14
5. Sampling and Analytical Procedures 17
THC, Benzene, Methane, and Ethane 17
C02, 02, and CO 17
TOA 18
Total Aldehydes and Formaldehydes 18
NOX 18
Duct Temperature, Pressure, and Velocity 19
Appendices
A. Representative Sample GC Plots 20
B. Audit Sample Results 27
C. Field Data 30
D. Draft EPA Benzene Method 46
E. LAAPCD Total Organic Acids Method 61
F. LAAPCD Aldehydes and Formaldehyde Methods 66
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TABLES
I
No. Page
1 Summary of Results - Benzene and Total Hydrocarbons 3
2 Summary -of Results - Miscellaneous Hydrocarbon Data 4
3 Summary of Results - Audit Samples . 4
4 Summary of Results - CO Data 5
5 Summary of Results - Total Organic Acids 6
6 Summary of Results - Total Aldehydes and Formaldehyde 7 .
7 Summary of Results - NO Data 8
X
8 Summary of Results - Duct Flow and Temperature Data 9
9 Process and Incinerator Operation Data 12
10 Sample Point Location - Outlet Duct: 16
FIGURES
No. Page
1 Incinerator Combustion Chamber 13
2 Sampling Site - Denka Chemical Corporation, Houston, Texas . . 15
VI
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SECTION 1
INTRODUCTION
This report presents the results of source testing performed during the
period March 20 to 24, 1978, by Midwest Research Institute (MRI) on the maleic
anhydride pliant, of the Denka Chemical Corporation, Houston, Texas. The facil-
ity is a typical maleic anhydride plant by the partial oxidation of benzene
process. The process includes aj?et scrubber for produc_t_je_covery. The ef-
fluent gases are then passed through an incinerator for hydrocarbon emission
control to the atmosphere via a 15.2 m (50 ft) stifck"^~ ~~ ;
Testing was done before and after the incinerator during periods of nor-
mal process operation. Inlet testing was done for benzene, total hydrocarbons
(THC), carbon dioxide (C02), oxygen (02), carbon monoxide (CO), methane, eth-
ane, total organic acids (TOA), total aldehydes, formaldehyde, temperature,
and duct pressure. Outlet testing was done for benzene, THC, methane, ethane,
C02, 02, CO, TOA, total aldehydes, formaldehyde, nitrogen oxides (NOX), tem-
perature, duct pressure, and duct volumetric flow. Portions of the gas sam-
ples were given to Denka personnel following MRI analysis so that they could
also perform the analyses. Their results are not included in this report.
The results of these tests are to be used in the establishment of emis-
sion standards for this industry.
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SECTION 2
SUMMARY AND DISCUSSION OF RESULTS
The results of the analyses for benzene and total hydrocarbons are shown
in Table 1. In all test runs, benzene was the primary component found. How-
ever, several additional peaks were measured in some of the samples. A list
of these peaks is given in Table 2. The compounds listed for peaks 2 through
6 and 8 are possibilities only (peak 7 was benzene). The tentative identifi-
cations are based upon retention index data provided by Dr. Joseph E. Knoll,
QAB/EMSL, Environmental Protection Agency, Research Triangle Park (EPA/RTP).
Many of the peaks are probably present in the ambient air or are outgassing
products from the sample bags. Peak 3 was a very broad peak which was not
resolved well. The width of this peak indicates a highly .polar compound such
as maleic acid. Examples of representative gas chromatograph (GC) plots for
the samples may be found in Appendix A.
The results of the audit samples may. be found in Table 3. The MRI and
Research Triangle Institute (RTI) values are presented. The audit report it-
self is in Appendix B. The MRI values in Table 3 and Appendix B differ because
of recalculations based on all of the acquired data being done after return to
Kansas City. The calibration curves used in the field assumed that the response
outside the calibration range continued curving at the same rate. Tests run
after returning indicate that much of the apprent curvature was due to random
errors of the calibration gases. The later calculated values assume that
points outside the calibration range have the same relative response as the
nearest calibration point.
The carbon monoxide analysis results are given in Table 4. The values
reported are minimum concentrations. The highest calibration gas mixture
available was 500 ppm carbon monoxide and the instrument response is known to
be slightly nonlinear at high concentrations.
The TOA results are presented in Table 5. The data are presented both
as acetic acid and as maleic acid. The field data may be found in Appendix C.
The total aldehyde and formaldehyde results are given in Table 6, while
the NO data are presented in Table 7.
Table 8 presents a summary of the duct flow and temperature measurements
made during the test series.
2
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TABLE 1. SUMMARY OF RESULTS - BENZENE AND TOTAL HYDROCARBONS
Date
March 21,
1978
March 22,
1978
March 23,
1978
Site
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Run
No.
1
1
2
2
3
3
(ppm)a/
780
11.1
820
11.8
940
14.4
Benzene
Benzene
Ib/hrt/
339 .
4.8
355
5.4
407
6.4
kg/l.r£/
154
2.2
161
2.4
185
2.9
(PPm)2/
830
12.9
950
12.4
1,070
14.3
1
Benzene
Ib/hrP./
360
5.3
412
5.7
463
6.4
Total Hydrocarbons
Propane
kg/hr£/
164
2.4
187
2.6
210
2.9
(ppm)±'
1,520
24.3
1,880
23.6
2,090
26.5
lb/hrl/
373
5.9
460
6.1
511
6.7
kg/hrl/
169
2.7
209
2.8
232
3.0
Benzene/
THC
ratio
0.940
0.860
0.863
0.952
0.879
al Parts per million (volume/volume) as benzene.
b/ Pounds per hour, as benzene.
cl Kilograms per hour, as benzene.
Al Parts per million (volume/volume) as propane.
e_/ Pounds per hour, as propane.
Jf/ Kilograms per hour, as propane.
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TABLE 2. SUMMARY OF RESULTS - MISCELLANEOUS HYDROCARBON DATA
Peak
No.
1
2
3
4
5
6
7
8
9
Compound^/
Methane, ethane,
Acetaldehyde
Maleic acid
Methanol, ethanol
Acetone, cyclo-
hexane
Acetonitrile
Benzene®./
Isobutanol, thio-
phene
Toluene
Retention
index
100-300
560
~ 600
630
660
680
750
810
Run
Inlet
lOb/
3
NR!/
0.4
0.4
0.4
ND
0.4
No. 1
Outlet
3
ND£/
NR
2
ND
ND
ND
ND
Run
Inlet
5
0.2
NR
Trace
0.4
0.4
0.4
10
No. 2
Outlet
3
ND
ND
ND
ND
ND
ND
ND
Run
Inlet
4
4
NR
10
3
1
ND
2
No. 3
Outlet
5
ND
ND
7
ND,
ND
ND
ND
a/ Tentative identification based on retention index data only.
b_/ Parts per million (volume/volume) as propane.
£/ ND = Not detectable.
d_/ NR = Peak present but very broad and not readable.
e/ See Table 1.
. TABLE 3. SUMMARY OF RESULTS - AUDIT .SAMPLES
Audit Sample
No.
B-1117
B-1529
RTI results
benzene!!/
(ppm)
101
387
MRI results
benzene^/
(ppm)
112
418
Audit accuracy
(%)k/
-10.89
-8.01
a_/ Parts per million (volume/volume) as benzene.
b/ Audit accuracy (%) = (RTI value-MRI value) 100
RTI value
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TABLE 4. SUMMARY OF RESULTS - CO DATA
Data
March 21,
1978
March 22,
1978
March 23,
1978
Site
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Run
No.
1
1
2
2
3
3
ppm£/
> 2,000
> 1,060
> 1,070
>2,130
> 1,990
> 950
CO
% by volume
> 0.2
> 0.1
>0.1
>0.2
> 0.2
> 0.1
Ib/hrt/
312
164
166
350
309
152
kg/hr
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TABLE 5. SUMMARY OF RESULTS - TOTAL ORGANIC ACIDS
Concentration, total organic acids
Date
March 21,
1978
March 22,
1978
March 23,
1978
Run
No.
1
1
2
2
3
3
As acetic acid
Site
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
gr/dscf3/
0.034
0.082
0.047
0.020
0.064
0.013
lb/hr*/
10.4
24.9
14.4
6.6
19.5
4.1
mg/dscm0-'
78
188
108
46
146
30
kg/hrl/
4.7
11.3
6.5
3.0
8.8
1.9
gr/dscf
0.067
0.158
0.091
0.039
0.123
0.025
As maleic acid
Ib/hr
20.5
48.1
27.8
12.7
37.5
7.9
mg/dscm
153
362
208
89
281
57
kg/hr
9.3
21.8
12.6
5.8
17.0
3.6
aj Grains per dry standard cubic foot.
b_/ Pounds per hour.
£/ Milligrams per dry standard cubic meter.
d_/ Kilograms per hour.
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TABLE 6. SUMMARY OF RESULTS - TOTAL ALDEHYDES AND FORMALDEHYDE
Total aldehydes
Date
March 21,
1978
March 22,
1978
March 23,
1978
Run
No.
1
1
2
2
3
3
Site
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
Ib/dacfS.'
(x 1(T7)
21.2
2.9
31.0
3.8
56.2
2.9
Ib/hrt
4.5
0.6
6.6
0.9
12.0
0.6
mg/dscm?.'
33.9
4.7
49.7
6.2
90.1
4.7
kg/hri/
2.0
0.3
3.0
0.4
5.4
0.3
Ib/dscf
(x 10-7)
6.9
0.4
13.6
0.0
29.9
0.4
Forma Idehyde
Ib/hr
1.48
0.09
2.91
0.00
6.39
0.09
mg/dscm
11.0
00.6
21.8
0.0
47.8
0.6
kg/hr
0.67
0.04
1.32
0.00
2.90
0.04
a/ Pounds (x 10"') per dry standard cubic foot.
])/ Pounds per hour.
cj Milligrams per dry standard cubic meter.
d/ Kilograms per hour.
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TABLE 7. SUMMARY OF RESULTS - NO DATA
oo
Date Site
March 21, Outlet
1978
March 22, Outlet
1978
March 23, Outlet
1978
Run
No. Sample
1 1
2
3
Average
2 1
2
3
Average
3 1
2
3£/
Average
Ib/dscf (x 10-7)£/
9.2
9.1
11.0
9.8
12.1
9.9
10.5
10.8
8.3
9.5
7.7£/
8.5
NOX
lb/hrk/
2.0
1.9
2.3
2.1
2.7
2.2
2.4
2.4
1.8
2.1
1.7S/
1.9
mg/dscm£'
14.7
14.6
17.6
15.7
19.5
15.9
16.8
17.4
13.3
15.2
12. 4£/
13.6
kg/hr^-/
0.9
0.9
1.0
1.0
1.2
1.0
1.1
1.1
0.8
1.0
0.8e/
0.9
a/ Pounds (x 10~?) per dry standard cubic foot.
b_/ Pounds per hour.
£/ Milligrams per dry standard cubic meter.
d/ Kilograms per hour.
e/ Portion of sample spilled during recovery; value may be unreliable.
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TABLE 8. SUMMARY OF RESULTS - DUCT FLOW AND TEMPERATURE DATA
Barometric
Date
March 21,
1978
March 22,
1978
March 23,
1978
Run
No.
1
1
2
2
3
3
pressure
Site
Inleti/
Outlet
Inleti/
Outlet
Inlet^
Outlet
mm Hg2/
,766
766
768
768
764
764
in . Hg— '
30.16
30.16
30.22
30.22
30.06
30.06
7. Mois-
ture
(% by
volume)
6.8
11.7
4.4
12.2
5.3
12.3
Stack
temperature
°c£/
41
174
41
152
39
179
-,Fd/
105
345
105
325
102
355
t
Stack
Static pressure
mm Hg
5.6
0.5
6.0
0.5
5.8
0.5
in. \\2<£-f
3.00
0.27
3.20
0.28
3.10
0.28
velocity
raps—'
12.88
12.79
12.50
13.37
12.61
13.57
fpm&/
2,535
2,519
2,460
2,631
2,482
2,672
Stack flow rate
dscmmb/
1.011.3
1,003.6
1,009.2
1,065.5
1,008.5
1,041.1
dscfmi/
35,713
35,443
35,638
37,628
35,614
36,766
a/ Millimeters mercury.
b/ Inches mercury.
£/ Degrees Centigrade.
d/ Degrees Fahrenheit.
e_/ Inches water.
il Meters per second.
j»/ Feet per minute.
h_/ Dry standard cubic meters per minute.
il Dry standard cubic feet per minute.
J/ Assumes 16 sq ft (1.49 sq in) cross-sectional area.
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SECTION 3
PROCESS DESCRIPTION AND OPERATION^/
The Denka maleic anhydride facility has a nameplate capacity of 23,000
Mg per year (50 million pounds per year). The plant was designed by Scientific
Design and purchased from Petro-Tex Chemical Corportation on July 1, 1977.
The plant was operating at about 70% of capacity when the sampling was con-
ducted; the plant personnel did not think that the lower production rate would
seriously affect the validity of the results.
The plant consists of a single train of equipment, with the exception of
multiple reactors and condensation equipment. Maleic anhydride is produced
by the following vapor -phase chemical reaction:
H\
C — C
- - II ° + 2H2O + 2CO2
.C— C
Benzene Oxygen Maleic Water Carbon
Anhydride Dioxide
A mixture of benzene and air enters a tubular reactor where the cata-
lytic oxidation of benzene is carried out. The reactor feed mixture is pro-
vided with excess air to keep the benzene concentration below its explosive
limit of 1.5 volume percent. The resultant large volume of reactor exhaust
directly influences the size of the subsequent product recovery equipment.
After reaction, the stream passes through a cooler, partial condenser, and
spearator in which a portion of the maleic anhydride is condensed and sepa-
rated as a crude product. The remaining product and other organics enter
the product recovery absorber where they are contacted with water or aqueous
maleic acid. The liquid effluent from the absorber is about a 40 weight per
cent aqueous solution of maleic acid. The absorber vent is directed to the
incinerator.
a/ This section furnished by EPA.
10
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The maleic acid is dehydrated by azeotropic distillation with xylene.
Any xylene retained in the crude maleic anhydride is removed in a xylene
stripping column, and the crude maleic anhydride from this column is then
combined with the crude maleic anhydride from the separator. The crude maleic
anhydride is fed to a fractionation column which yields purified molten maleic
anhydride as the overhead product. The fractionation column bottoms contain-
ing the color-forming impurities are removed as liquid residue waste.
Essentially all process emissions will exit through the product recovery
absorber. These emissions will include any unreacted benzene, which can con-
stitute 3 to 7% of the total benzene feed. The only other process emission
source is the refining vacuum system vent, which can contain small amounts of
maleic anhydride, xylene, and a slight amount of benzene, since benzene could
be absorbed in the liquid stream from the product recovery absorber or in the
crude maleic anhydride from the separator.
Table 9 summarizes data on the process and incinerator operation during
the sampling runs. There were no process upsets during the sampling effort.
The following relation was provided to convert the waste gas flow rate
in pounds per hour to SCFH by Denka:—
Vol. Flow rate, SCFH = (Mass flow rate, Ib/hour)(1.03)(359 SCF/mole)
MW of air
= (160,800)(1.03)(359)
29
= 2.05 x 106 SCFH
= 34,000 SCFM
Where 1.03 is a meter factor (standard conditions are 32°F and 30 in. Hg).
o
The size of the combustion chamber is 2,195 ft . There are three thermo-
couples used to sense the flame temperature, and these are averaged to give
the temperature recorded in the control room. A rough sketch of the combustion
chamber is provided in Figure 1.
a/ MRI used the following, similar equation:
Vol. flow rate, SCFH = (Mass flow rate, lb/hour)(24 //g-mole)(453.4 ]|Imole )
(28.3 ^/SCF)(Dry mol. wt. stack gas, lb
Ib-mole
(std. conditions of 68°F and 29.92 in. Hg),
11
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TABLE 9. PROCESS AND INCINERATOR OPERATION DATA
Parameter
Production Rate (Ib/hour)
Natural Gas Flow Rate (SCFH at 145 psig)
Incinerator Temperature ( °F)
Supplemental Combustion Air Flow Rate
Sample
No. 1
4,200
63,000
1,400
51,300
Sample
No. 2
4,200
64,000
1,400
51,300
Sample
No. 3
4,200
64,000
1,400
51,300
(Ib/hour at 80°F)
,_, Waste Gas Flow Rate to the Incinerator
10 (Ib/hour)
Rate of Steam Production (Ib/hour at 736°F)
160,800
54,000
160,800
55,000
160,800
55,000
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12ft
-15ft, 6in-
Flow
Side View
23ft.3.5in-
17ft, 6in
(Outlet)
There are three thermocouples spaced evenly across the
top of the firebox.
The width of the firebox is 6ft, 6in.
Figure 1. Incinerator Combustion Chamber
13
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SECTION 4
LOCATION OF SAMPLE POINTS
Figure 2 presents a schematic of the overall sampling site. The single
inlet sampling port was located in an expansion between a 0.91 m (36 in.) di-
ameter duct and the incinerator. No additional ports could be established
any of the inlet ducting. The inlet was sampled using a 1.27 cm (0.5 in.) ID
stainless steel tube whose tip was 0.53 m (21 in.) into the duct.
The eight outlet ports were located five to six diameters downstream of
any disturbances. For the velocity traverse, 48_pjp_ints were used. These
point locations are presented in Table 10.
14
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To Gas Sampl
To TOA Sample-
»- 1 " Valve
T i/T~^
k- 36"-*) -
^'
\^ J
x
H 4' — H
b. Incinerator Inl
Bypass
Process
Vent
(^ ^^p^-H
k_
Process • OQ"
e
(4 . / • ^1
t I ::
-4' 4' 3.
1 1 ':
i 112345678
^ HRF=IRRRRRP
X 3" ID Ports /
et c. Incinerator Outlet
Ports
r r\
r
1 '
)
fc- Flow . Flow — ^
~ 15'
1 '
— • "V. IIICIIKSIUIUI
| \- Platform
Insulation
*'
\
\
\
&u ^
\
\
t
^
b
35'
a. Schematic of Site Layout
Figure 2. Sampling site - Denka Chemical Corporation, Houston, Texas.
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TABLE 10. SAMPLE POINT LOCATION - OUTLET DUCT
Duct size: 1.22 x 1.83 m (4 x 6 ft)
Distance from inside wall
Traverse point cm in.
1 10.2 4
2 30.5 12
3 50.8 20
4 71.1 28
5 91.4 36
6 111.8 44
16
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SECTION 5
SAMPLING AND ANALYTICAL PROCEDURES
THC, BENZENE, METHANE, AND ETHANE
The gas samples were obtained according to the September 27, 1977,_E.PA_
Jraf.t_b_enz-ene_method,. (Appendix D). Seventy liter aluminized Mylar bags were
used with sample times of 2 to 3 hr. The sample box and bag were heated to
approximately 66°C (150°F) using an electric drum heater and insulation. Dur-
ing Run 1-Inlet, the variac used to control the temperature malfunctioned so
the box was not heated for this run. A stainless steel probe was inserted
into the single port at the inlet and connected to the gas bag through a "tee.1
The other leg of the "tee" went to the TOA train. A teflon line connected the
,bag and the "tee." A stainless steel probe was connected directly to the bag
at the outlet. The lines were kept as short as possible and not heated. The
boxes were transported to the field lab immediately upon completion of samp-
ling. They were heated until the GC analyses were completed.
A Varian model 2440 gas chromatograph with a Carle gas sampling valve
equipped with 2 cnP matched loops was used for the integrated bag analysis.
The SP-1200/Bentone 34 column was operated at 80°C. The instrument has a
switching circuit which allows a bypass around the column through a capillary
tube for THC response. The response curve was measured daily for benzene (5,
10, and 50 ppm standards) with the column and in the bypass (THC) mode. The
THC mode was also calibrated daily with propane (20, 100, and 2,000 ppm stan-
dards). The calibration plots showed moderate nonlinearity. For sample read-
ings which fell within the range of the calibration standards an interpolated
response factor was used from a smooth curve drawn through the calibration
points. For samples above or below the standards the response factor of the
nearest standard was assumed. THC readings used peak height and column read-
ings used area integration measured with an electronic "disc" integrator.
C02, 02, AND CO
Analysis for these constituents was done on samples drawn from the inte-
grated gas bag used in THC, benzene, methane, and ethane. Carbon monoxide
analysis was done following the GC analyses using EPA Reference Method 10
17
-------
(Federal Register, Vol. 39, No. 47, March 8, 1974). A Beckman Model 215 NDIR
analyzer was used. Analyses were done on both the inlet and outlet samples.
Orsat analysis was performed to determine the carbon dioxide and oxygen
fractions. Denka has requested that the COo data from the incinerator inlet
be termed "confidential." EPA is honoring this request until such time the
data are determined to be nonconfidential. The 02 and C02 data are being filed
under separate cover.
TOA
The total organic acid samples were obtained according to the Los Angeles
Air Pollution Control District (LAAPCD) method (Appendix E). The inlet sample
was run from a "tee" on the integrated gas probe while the outlet sample was
obtained from port No. 3. Sample times varied from 2 to 3 hr with a flow rate
of approximately 14.1 liters/min (0.5 ft^/min).
/
The samples were recovered in the field lab, transferred to glass bottles,
and trucked to MRI for analysis.
TOTAL ALDEHYDES AND FORMALDEHYDE
These samples were obtained from the integrated bag samples from the THC,
benzene, methane, and ethane section. The LAAPCD method was used for each
(Appendix F). Two flask samples were obtained from each bag sample. The sam-
ples were recovered in the field lab, transferred to glass bottles, and trucked
to MRI for analysis. One flask sample per run was used for the aldehyde analy-
sis and one was used for the formaldehyde analysis.
N0x
NOX samples were obtained according to EPA Reference Method 7 (Federal
Register. Vol. 42, No. 160, August 18, 1977). Three samples per run were ob-
tained from the outlet stack. Samples were taken from ports 2 and 3.
The samples were recovered in the field lab, transferred to shipping bot-
tles, and trucked to MRI for analysis.
18
-------
DUCT TEMPERATURE, PRESSURE, AND VELOCITY
Duct temperature and pressure values were obtained from the existing
inlet port. A thermocouple was inserted into the gas sample probe for the
temperature while a water manometer was used for the pressure readings. These
values were obtained at the conclusion of the sampling period.
Temperature, pressure, and velocity values were obtained for the outlet
stack. Temperature values were obtained by thermocouple during the gas samp-
ling. Pressure and velocity measurements were taken according to EPA Reference
Method 2 (Federal Register. Vol. 42, No. 160, August 18, 1977). These values
also were obtained at the conclusion of the sampling period.
19
-------
APPENDIX A
REPRESENTATIVE SAMPLE GC PLOTS
20
-------
I I
4567
Time, Minutes
Run 1 - Inlet
21
10
11
-------
I
0
3456
Time, Minutes
Run 1 - Outlet
8
22
-------
0
456
Time, Minutes
Run 2 - Inlet
23
.8
10
-------
I
1.
345
Time, Minutes
Run 2 - Outlet
24
-------
o
3456
Time, Minutes
Run 3 - Inlet
25
-------
I I
I
I
I
345
Time, Minutes
Run 3 - Outlet
26
8
-------
APPENDIX B
AUDIT SAMPLE RESULTS
27
-------
AUDIT REPORT
PART A - (Filled out by RTI) .
1. ESED, EHB Project Officer Denn'i's'Hol'zschuh
2. Location Where Audit Cylinders Shipped Midwest Research institute
425 Volker Blvd., Kansas City, Missouri 64110•
3.
4.
Planned Shipping Date for Cylinders March i. 1978
Details on Audit Cylinders
A. Cylinder Number
B. Cylinder Pressure, PSI
C. Cylinder Concentration, ppm
D. Date of Cylinder Analysis
Benzene
Low Cone.
Cylinder
' B-1117
' "2000
' 101
' 2/8/78
High Cone.
Cylinder
B-1529
1900
387
2/9/78
PART B - (Filled out by ESED, EMB Project Officer)
5. Type of Organic Manufacturing Process ' ' 'f^a. le.i c ///u />/ o) n o
6. Location of Audit
v^'kw 'C_ Ae^'/'eer / ^
— i
u t AQK/ . /e
7. . Name of Individual Audited and Organization G> e o r-g e 0 c A e i /
5-j-
_ ' ' ' rv":Vc' i^'e.^ f?e..c ^c.r^ii ' / o v // /"o rC.
28
-------
AUDIT REPORT (Continued)
8. Audit Results
Low Cone. High Cone.
Cylinder Cylinder
A. Cylinder Number ft -//
-. B. Cylinder Pressure Before / ytf
* Calculate % Accuracy = Cone. RTI - Cone Measured ^ 10Q
wOJlC » f\ J. -L
G. Description of Problems Detected
29
-------
APPENDIX C
FIELD DATA
30
-------
MIDWEST RESEARCH INSTITUTE
RUN
MRI Project Number 6>'g>- L 5
Field Dates ^O-d^ M+z ~7&
Plant De^ be.
Sampling Location /frka
Sampling Date 3 |
FIELD CREW
Crew Chief //l*)X.uJet,L- _ __
Testing Engineer 1
Engr. Technician 1
Lab Technician
2 Cot-G
Process Engineer 1
Other 1
2.
MRI - Form PO (10/72) 31
-------
FIELD DATA
-------
FIELD DATA
PLANT
HATF
^. H o
PROBE HEATER SETTING.
HEATER BOX SETTING
REFERENCE ip
-V "
~^( a
SCHEMATIC OF TRAVERSE POINT LAYOUT
Co
READ AND RECORD ALL DATA EVERY
TRAVERSE
POINT
NUMBER
\ 5- cr\
^
\. CLOCK TIME
"~ " ' __
H Or;
15" 11
15 21-7
/^ $ 7
/L, ^L
/7/7
/7Z-?
GAS METER READING
ivm». it3
8 1 1 . ri e> ^^^"
5b/o. o°i
S3d7.^^>
5^ ~? . 7 £-
£6&-S£-
•
VELOCITY
HEAD
UPSI. in. H^O
ORIFICE PRESSURE
DIFFERENTIAL
am. in. H?0l
DESIRED
. 55-
. ~io
.70
,' Ic
ACTUAL
MINIIT
STACK
TEMPERATURE
«T$.."F
$*{
IMPINGER
TEMPERATURE.
"F
•
r I
'~.~>
-------
PRELIMINARY VELOCITY TRAVERSE
:~c*.
?LANT_LL'
DATE .of
LOCATION ? (^. *-1 - •*
STACK I.D. XV X- r^ -£/"•
BAROMETRIC PRESSURE, in. Hg
STACK GAUGE PRESSURE, in. H..Q -/--J"7
OPERATORS /•t-faxt.tJfe.f, Wr-xL.i
•\ 3 - e? .
I A
TRAVERSE
POINT
NUMBER
(-1
^
*>
*(
4
(*
^-^
2
3
' <
*>
(«
^-(
2
3
x/
•7
6
4-/
2_
t
4
$
&
AVERAGE
VELOCITY
HEAD
kps),in.H20
.1^
. (1
.^/
^7
.tr-o
.41
_l-7
-
-'If
-S'*.
. 6^
.67
-O
. He
* 3(s>
.. 3/
^~l
^~l
STACK
TEMPERATURE
(Ts), °F
5H^
• LJ
r
: *'
t*
' SCHEMATIC OF TRAVERSE POINT LAYOUT
S
TRAVERSE
POINT
NUMBER
£?-(
2~
£,
*?
y
fa
6^?-
^
^
"?
9
c
7 -/
^
5
<7
^
6
^ -/
^
^
f
^'
<~
AVERAGE
VELOCITY
HEAD
»M
,33.
.41
,S~o
,5-3
.4*7
- /5~
.^&
,3^
.5^-'
..6/
,s^
- 1°)
^f.55
^j
- S5-
. 55~
t b^
l*t
,7^
,^c;
-b"/
,4<7
^4>"
, '^l
STACK
TEMPERATURE
(Ts), °F
_^^^~
^^"
EPA (Dur) 233
472
34
-------
*un Number
Date
MIDWEST RESEARCH INSTITUTE
NOX SAMPLING
PROBE
Unit No. Length =
5"
Lining
Material
ft D S. Steel
EJ Pyrex
Pre-Filter
Pitot
Heated Tube
Glass Wool HI Yes No.
SAMPLING DATA
Flask No.
Volume of Flask
Less Absorb. Soln.
Initial Conditions:
Barometric Pressure (in. Hg)
Flask Temperature (°F)
Flask Vacuum (in. Hg):
Top
Bottom
Difference
Leak Check
Sampling Location:
Port
Point or Distance from
Inside of Port
Clock Time
Performed by
Comments:
A/7
6-
No Coefficient:
Q .ss r
A/-33-
- z
MRl-FORM G8/9-NOx (6/72)
-------
MIDWEST RESEARCH INSTITUTE
MRI Project Number
Field Dotes la -Z4
Plant
Sampling Location
Sampling Date 33.
Crew Chief
Testing Engineer 1
Engr. Technician 1
Lab Technician
Process Engineer 1
2
Other 1
2.
RUN
/e •
FIELD CREW
MRI - Form PO (10/72)
36
-------
„.„
zzn
SAMPLING LOCATION
SAMPLE TYPE _
RUN NUMBER _
OPERATOR
FIELD DATA
4014
PROBE LENGTH AND TYPE.
NOZZLE I.D
AMBIENT TEMPERATURE
BAROMETRIC PRESSURE
STATIC PRESSURE, i
FILTER NUMBER'si
-U
ASSUMED MOISTURE. % .
SAMPLE BOX NUMBER.
METER BOX NUMBER _
METER AHt
CFACTOR.
CCV.V.ENTS
IFA.Dur. 715
1 ;.'
-------
FIELD DATA
PLANT.
DATE_
Uz>>
PROBE LENGTH AND TYPE.
NOZZLE 1.0
SAMPLING LOCATION.
SAMPLE TYPE
RUN NUMBER 2
OPERATOR /rt^
AMBIENT TEMPERATURE
BAROMETRIC PRESSURE .
STATIC PRESSURE. iP$i_
FILTER NUMBER is>
ASSUMED MOISTURE.'..
SAMPLE BOX NUMBER,
METER BOX NUMBER _
METER JkH<,
CFACTOR.
PROBE HEATER SETTING.
HEATER BOX SETTING
REFERENCE ip
SCHEMATIC OF TRAVERSE POINT LAYOUT
READ AND RECORD ALL DATA EVERY
CO.WIENTS
-------
PRELIMINARY VELOCITY TRAVERSE
PLANT.
DATE 33. A\A^ 7%
LOCATION C'K-Vle\
STACK I.D. 4 ' X. (j> '
BAROMETRIC PRESSURE, in. Hg .."b&,C.
STACK GAUGE PRESSURE, in. H?Q 4 O.
OPERATORS.
SCHEMATIC OF TRAVERSE POINT LAYOUT
TRAVERSE
POINT
NUMBER
8-/
z.
5
^
6
•6?
?-/
Z.
3
f
5
(s
(*-(
2_
^
-T
^
u>
t~ 1
L
3
^
5
G
AVERAGE
VELOCITY
HEAD
(Aps), in.H20
_/5"~
.32
-^7
.55"
. ^
. 5~/
- ^
^ 3e>
.^
.6^
.^z-
,13~6?
.JrT
^2?
,44
.63
,6?7
./,7
. i7
,^
.<13
r5"?>
,£<^
/^
STACK
TEMPERATURE
(Ts), °F
1- '
fr»
TRAVERSE
POINT
NUMBER
^-f
a
5
^
5
b
3-1
Z
5
-• <
^
c?
P-f
Z
3
^
9
G
f-(
Z.
^
^
4
5
L
AVERAGE
VELOCITY
HEAD
(Aps), in.H20
,^3
.^0
-3/
,5°I
-5fe
«6?O
- (1
-^^
o 50
. 5^
.65
ifH
,!&
,3*
>n
^ 5^
.^/
.<^/
.(^
.;?/
/3
-------
Run Number
Date
1 ">
MIDWEST RESEARCH INSTITUTE
NOX SAMPLING
PROBE
Unit No. Length =
Lining
Material
Pre-Filter
Heated
Pitot
Tube
ft D S. Steel 0 Glass Wool d Yes No.
0 Pyrex r—i Q No Coefficient:
Flask No.
Volume of Flask
Less Absorb. Soln.
Initial Conditions:
Barometric Pressure (in. Hg)
Flask Temperature (°F)
Flask Vacuum (in. Hg):
Top
Bottom
Difference
Leak Check
Sampling Location:
Port
Point or Distance from
Inside of Port
Clock Time
Performed by
Comments:
A &
"
SAMPLING DATA
/I/ 7
10.12-
aw
2
1 5-5-5-
I*
a .
71
O.K.
/ CP
MRI-FORM G8/9-NOx (6/72)
40
-------
MIDWEST RESEARCH INSTITUTE
MRI Project Number
Field Dates £ -?*{
Plant
Sampling Location /He, !<£.,-<,
Sampling Date .
Testing Engineer 1
Engr. Technician. 1
3^
Lab Technician 1
Other
2.
Process Engineer 1 <5u M"
RUN 3
FIELD CREW
Crew Chief
MRI - Form PO (10/72) 41
-------
FIELD DATA
ro
TRAVERSE
i POINT
: NU.VBER
i
j
.
i
'
1
1
PLANT V/D "I I** l »
DATE OJ3 MAR • ?*
SAMPLING L(
SAMPLE TYP
RUN NUMBEF
OPERATOR
AMBIENT TE
BAROMETRIC
STATIC PRE!
FILTER NUM
X, CLOCK TIME
SAMPLING \ c'lOCKi
TIME mm "\_
fj"~~— —
r_ G^^Q
b 7~5V?
/o?io
/D50
—
f/s-o
(^."20
~ -
; !
1
3CATION f'hLfT
>
i —
>L
F T*ir€g. iSA^ c
,? X
L/\?W^6L^
V1PFRATURF ^5
PRFSSURE 3c.OO»
MIR? (Pi -t- 3>-l l'~. -flzO
BFBm
PROBE LENGTH AND TYPE
/2^/V"t fr&<
'o
NOZZLE 1.0
ASSUMED MC
SAMPLE BO)
METER BOX
METER AHa
C FACTOR
1
ISTIIRF •.
( NUMBER
NUMBER
~fil4l> "TEtHt^. PROBE HEATER SETTING
— *" HEATER BOX SETTING
,
C/i " Aj- 'o SCHEMATIC OF TRAVERS P(
*^ READ AND RECORD ALL DATA EV RY
GAS METER READING
-------
JkJsfe.——--
FIELD DATA
PLANT.
DATE.
SAMPLING LOCATION.
SAMPLE TYPE
RUN NUMBER .
OPERATOR
AMBIENT TEMPERATURE
BAROMETRIC PRESSURE .
STATIC PRESSURE. iPs>_
FILTER NUMBER i$i
PROBE LENGTH AND TYPE.
NOZZLE I.D
ASSUMED MOISTURE.'..
SAMPLE BOX NUMBER.
METER BOX NUMBER _
METER AHj,
C FACTOR ;
? to
PROBE HEATER SETTING.
HEATER BOX SETTING
REFERENCE ip
SCHEMATIC OF TRAVERSE POINT LAYOUT
TRAVERSE
POINT
NUMBER
f (;-
\ CLOCK TIME
^ - ,
Oci^i^>
READ AND RECORD ALL DATA EVERY MINUTES ' IQ fc
GAS METER READING
•V . II3
»«'• "
QJ&-^~7
107^ 41.00
/of 5
//Ao
iz> i
/
^
/
(
/
\
y
(
-f^SJ*
VwtJtJWT
) m..Hg
s-»
'..5.^.
93
cj/i
1
..._. . .
TEMPERATURE.
"F
[40
. /£> .
Ho
"" Wo
f if
( / -t^-C
&J54
- '/4%-
//2.0
/Z- tv '•
IZz'H
i
\
,
t
._ _ 1 1 - _ '
" j~ r~ i"'"" rr~ •
I i
i
i
J_
- t>
COV..VENTS
A.O^t .'3S
-------
PRELIMINARY VELOCITY TRAVERSE
PLANT.
DATE_
LOCATION Q^VUK
STACK I.D. ^' x. & '
BAROMETRIC PRESSURE, in. Hg
STACK GAUGE PRESSURE, in. H.O 4- O, .?£, U. 4-Lp
OPERATORS.
SCHEMATIC OF TRAVERSE POINT LAYOUT
TRAVERSE
POINT
NUMBER
ft - (
2.
3
-r
*>
k
1-1
Z
*
1
5
(«
(. -(
*
3
-------
Run Number
Date -?/"
MIDWEST RESEARCH INSTITUTE
NOX SAMPLING
PROBE
Unit No. Length =
Lining
Material
ft D S. Steel
(2 Pyrex
Pre-Filter
Glass Wool
Pitot
Heated Tube
Yes No.
Flask No.
Volume of Flask
Less Absorb. Soln.
Initial Conditions:
Barometric Pressure (in.
Flask Temperature (°F)
Flask Vacuum (in. Hg):
Top
Bottom
Difference
Leak Check
Hg)
-^0**^-
Sampling Location:
Port
Point or Distance from
Inside of Port
Clock Time
Performed by
Comments:
No Coefficient:
a .85
SAMPLING DATA
-30,
13
HO*
(,*
3-1
MRI-FORM G8/9-NOx (6/72)
45
-------
APPENDIX D
DRAFT EPA BENZENE METHOD
46
-------
L'ifcrl CiM 27 SEP B//
METHOD . DETERMINATION OF BEMZEMF
FROM STATIONARY SOURCES
INTRODUCTION y
Performance of this method should not be attempted
by persons unfamiliar with the operation of a gas
chromatograph, nor by those who are unfamiliar with
source sampling, as there are many details that are
beyond the scope of this presentation. Care must
be exercised to prevent exposure of sampling personnel
to benzene, a carcinogen.
1. Principle and Applicability . .
1.1 Principle. An integrated bag sample of stack gas containing
benzene and other organics is subjected to gas chromatographic (GC)
analysis, using a flame ionization detector (FID).
1.2 Applicability. The method is applicable to the measurement
of benzene in stack gases only from specified processes. It is not
•
applicable where the benzene is contained in particulate matter.
2. Range and Sensitivity
The procedure described herein is applicable to the measurement
pf benzene in the 0.1 to 70 ppm range. The upper limit may be
extended by extending the calibration range or by dilution of the
sample.
3. Interferences
The chromatograph columns and the corresponding operating
parameters herein described have been represented as being useful for
producing an adequate resolution of benzene. However, resolution
interferences may be encountered on some sources. Also, the chro-
matograph operator may know of a column that will produce a superior
47
-------
resolution of benzene without reducing the response to benzene
as specified in Section 4.3.1.
In any event, the chromatograph operator shall select a
column v/hich is best suited to his particular analysis problem,
subject to the approval of the Administrator. Such approval shall
be considered automatic provided that confirming data produced
through a demonstrably adequate supplemental analytical technique,
such as analysis with a different column or g.c./mass spectroscopy,
is available for review by the Administrator.
4. Apparatus
4.1 Sampling (see Figure 1).
4.1.1 Probe. Stainless steel, Pyrex glass, or Teflon tubing
•
according to stack temperature, each equipped with a glass wool plug
to remove particulate matter.
4.1.2 Sample Line. Teflon, 6.4 mm outside diameter, of sufficient
length to connect probe to bag. A new unused piece is employed for
each series of bag samples that constitutes an emission test.
4.1.3 Male (2) and female (2) stainless steel quick connects,
with ball checks (one pair without) located as shown in Figure 1.
4.1.4 Tedlar or aluminized Mylar bags, 100 liter capacity. To
contain sample.
4.1.5 Rigid leakproof containers for 4.1.4, with covering to
protect contents from sunlight.
Mention of trade nair.es on specific products does not constitute
endorsement by the Environmental Protection Agency.
48
-------
STACK WALL
FILTER (GLASS WOOL) .'
1
QUICK
CONNECTS
FEMALE
_„ TEDLAR:
BAG
OR
ALUMINIZED
MYLAR
TEFLON
•SAMPLE LINE
RIGID LEAK-PROOF
CONTAINER
Figure :1. Integrated-bag sampling train. (Mention of trade .names on specific products .
does not constitute endorsement by the Environmental Protection Agency.)
49
-------
4.1.6 Needle Valve. To adjust sample flow rate.
4.1.7 Pump--Leak-free. Minimum capacity 2 liters per minute.
4.1.8 Charcoal Tube. To prevent admission of benzene and other
organics to the atmosphere in the vicinity of samplers.
4.1.9 Flow Meter. For observing sample flow rate; capable of
measuring a flow range from 0.10 to 1.00 liters per minute.
4.1.10 Connecting Tubing. Teflon, 6.4 mm outside diameter, to
assemble sample train (Figure 1).
4.2 Sample Recovery.
4.2.1 Tubing. Teflon, 6.4 mm outside diameter, to connect bag to
gas chromatograph sample loop. A new unused piece is employed for each
series of bag samples that constitutes an emission test, and is to be
discarded upon conclusion of analysis of those bags.
4.3 Analysis.
4.3.1 Gas Chromatograph. With FID, potentiometric strip chart
recorder and 1.0 to 2.0 ml heated sampling loop in automatic sample
valve. The chromatographic system shall be capable of producing a
response to 0.1 ppm benzene that is at least as great as the average
noise level. (Response is measured from the average value of the
baseline to the maximum of the waveform, while standard operating
conditions are in use.)
4.3.2 Chromatographic Column.
4.3.2.1 Benzene in the Presence of Aliphatics. Stainless Steel,
2.44 rn x 3.2 mm, containing 10 percent TECP on 80/100 Chrcmosorb P AW.
50
-------
4.3.2.2 Benzene With Separation of the Isomers of Xylene. Stainless
steel, 1.83 m x 3.2 mm, containing 5 percent SP-1200/1.75 percent Bentone
34 on 100/120 Supelcoport.
4.3.3 Flow Meters (2). Rotameter type, 0 to 100 ml/min capacity.
4.3.4 Gas Regulators. For required gas cylinders.
4.3.5 Thermometer. Accurate to one degree centigrade, to measure
temperature of heated sample loop at time of sample injection.
4.3.6 Barometer. Accurate to 5 mm Hg, to measure atmospheric
pressure around gas chromatograph during sample analysis.
4.3.7 Pump—Leak-free. Minimum capacity 100 ml/min.
4.3.8 Recorder. Strip chart type, optionally equipped with disc
integrator or electronic integrator.
4.3.9 Planimeter. Optional, in place of disc or electronic
integrator, for 4.3.8 to measure chromatograph peak areas.
4.4 Calibration. 4.4.2 through 4.4.6 are for section 7.1 which
is optional.
4.4.1 Tubing. Teflon, 6.4 mm outside diameter, separate pieces
marked for each calibration concentration.
4.4.2 Tedlar or Aluminized Mylar Bags. 50-liter capacity, with
valve; separate bag marked for each calibration concentration.
4.4.3 Syringe. 1.0 pi, gas tight, individually calibrated, to
dispense liquid benzene.
4.4.4 Syringe. 10 yl, gas tight, individually calibrated, to
dispense liquid benzene.
4.4.5 Dry Gas Meter, With Temperature and Pressure Gauges.
Accurate to +2 percent, to meter nitrogen in preparation of standard
gas mixtures.
-------
4.4.6 Midget Impinger/Hot Plate Assembly. To vaporize benzene.
5. Reagents
It is necessary that all reagents be of chromatographic grade.
5.1 Analysis.
5.1.1 Helium Gas or Nitrogen Gas. Zero grade, for chromatographic
carrier gas.
5.1.2 Hydrogen Gas. Zero grade.
5.1.3 Oxygen Gas or Air as Required by the Detector. Zero grade.
5.2 Calibration. Use one of the following options: either 5.2.1
and 5.2.2, or 5.2.3.
5.2.1 Benzene, 99 Mol percent pure benzene certified by the
manufacturer to contain a minimum of 99 Mol percent benzene; for use in
the preparation of standard gas mixtures as described in Section 7.1.
5.2.2 Nitrogen Gas. Zero grade, for preparation of standard gas
mixtures as described in Section 7.1.
5.2.3 Cylinder Standards (3). Gas mixture standards (50, 10, and
5 ppm benzene in nitrogen cylinders) for which the gas composition has
been certified with an accuracy of +3 percent or better by the
manufacturer. The manufacturer must have recommended a maximum shelf
life for each cylinder so that the concentration does not change
greater than +5 percent from the certified value. The date of gas
cylinder preparation, certified benzene concentration and recommended
jnaximum shelf life must have been affixed to the cylinder before ship-
ment from the gas manufacturer to the buyer. These gas mixture
standards may be directly used to prepare a chromatograph calibration
curve as described in Section 7.3.
52
-------
5.2.3.1 Cylinder Standards Certification. The concentration
of benzene in nitrogen in each cylinder must have been certified by
the manufacturer by a direct analysis of each cylinder using an
analytical procedure that the manufacturer had calibrated on the day
of cylinder analysis. The calibration of the analytical procedure
shall, as a minimum, have utilized a three-point calibration curve.
It is recommended that the manufacturer maintain two calibration standards
and use these standards in the following way: (1) a high concentration
standard (between 50 and 100 ppm) for preparation of a calibration curve
by an appropriate dilution technique; (2) a low concentration standard
(between 5 and 10 ppm) for verification of the dilution technique used.
5.2.3.2 Establishment and Verification of Calibration Standards.
The concentration of each calibration standard must have been established
•
by the manufacturer using reliable procedures. Additionally, each
calibration standard must have been verified by the manufacturer by one
of the following procedures, and the agreement between the initially
determined concentration value and the verification concentration value
must be within +5 percent: (1) verification value determined by com-
parison with a gas mixture prepared in accordance with the procedure
described in section 7.1 and using 99 Mol percent benzene, or (2) veri-
fication value obtained by having the calibration standard analyzed by
the National Bureau of Standards. All calibration standards must be
renewed on a time interval consistent with the shelf life of the cylinder
standards sold.
53
-------
6. Procedure
•^—^^ • ™ *~ , \_
6.1 Sampling. Assemble the sample train as in Figure 1. Perform
a bag leak check according to section 7.4. Determine that all connections
between the bag and the probe are tight. Place the end of the probe at
the centroid of the stack and start the pump v/ith the needle valve
adjusted to yield a flow of 0.5 1pm. After a period of time sufficient
to purge the line several times has.elapsed, connect the vacuum line to
the bag and evacuate the bag until the rotameter indicates no flow.
Then reposition the sample and vacuum lines and begin the actual sampling,
keeping the rate constant. Direct the gas exiting the rotameter away
from sampling personnel. At the end of the sample period, shut off the
pump, disconnect the sample line from the bag, and disconnect the
vacuum line from the bag container. Protect the bag container from
•
sunlight.
6.2 Sample Storage. Sample bags must be kept out of direct sunlight.
Analysis must be performed within 24 hours of sample collection.
6.3 Sample Recovery. With a new piece of Teflon tubing identified
for that bag, connect a bag inlet valve to the gas chromatograph sample
valve. Switch the valve to withdraw-gas from the bag through the sample
loop. Plumb the equipment so the sample gas passes from the sample valve
to the leak-free pump, and then to a charcoal tube, followed by a
0-100 ml/min rotameter with flow control valve.
6.4 Analysis. Set the column temperature to 80°C for column A or
75°C for column B, the detector temperature to 225°C, and the sample loop
temperature to 70°C. When optimum hydrogen and oxygen flow rates have
54
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been determined, verify and maintain these flow rates during all
chromatograph operations. Using zero helium or nitrogen as the.
carrier gas, establish a'flow rate in the range consistent with the
manufacturer's requirements for satisfactory detector operation. A
flow rate of approximately 20 ml/min should produce adequate separations.
Observe the base line periodically and determine that the noise level
has stabilized and that base line drift has ceased. Purge the sample
loop for thirty seconds at the rate of 100 ml/min, then activate the
sample valve. Record the injection time (the position of the pen on
the chart at the time of sample injection), the sample number, the
sample loop temperature, the column temperature, carrier gas flow rate,
chart speed and the attenuator setting. Record the laboratory pressure.
From the chart,'note the peak having the retention time corresponding to
benzene, as determined in section 7.2. Measure the benzene peak area, A ,
by use of a disc integrator or a planimeter. Record A and the
retention time. Repeat the injection at least two times or until two
'consecutive values for the total area of the benzene peak do not vary
more than 5 percent. The average value for these two total areas will
be used to compute the bag concentration.
6.5 Measure the ambient temperature and barometric pressure near
the bag. From a water saturation vapor pressure table, determine and •
record the v/ater vapor content of the bag. (Assume the relative humidity
to be 100 percent unless a lesser value is known.)
7. Calibration and Standards
7.1 Preparation of Benzene Standard Gas Mixtures. (Optional —
delete if cylinder standards are used.) Assemble the apparatus shown
55
-------
Ul
SYRINGE
BOILING
WATER
. BATH
SEPTUM:
V A
- MIDGET
IMPINGER
HOT PLATE
CAPACITY
50 LITERS
FIGURE 2. PREPARATION OF BENZENE STANDARDS
(optional)
-------
Record the injection time. Select the peak that corresponds to
,\'
benzene. Measure the distance en the chart from the injection time to
the time at which the peak maximum occurs. 'This quantity, divided by
the chart speed, is defined as the benzene peak retention time. Since
1t is quite likely that there will be other organics present in the
sample, it is very important that positive identification of the benzene
peak be made.
7.3 Preparation of Chromatograph Calibration Curve. Make a gas
chromatographic measurement of each standard gas mixture (described in
section 5.2.3 or 7.1) using conditions identical with those listed in
sections 6.3 and 6.4. Flush the sampling loop for 30 seconds at the
rate of 100 ml/min with one of the standard gas mixtures and activate the
sample valve. Record C , the concentration of benzene injected, the
attenuator setting, chart speed, peak area, sample loop temperature,
column temperature, carrier gas flow rate, and retention time. Record
the laboratory pressure. Calculate A , the peak area multiplied by the
attenuator setting. Repeat until two consecutive injection areas are
within 5 percent, then plot the average of those two values vs C . When
the other standard gas mixtures.have-been similarly analyzed and plotted,
draw a smooth curve through the points. Perform calibration daily, or
before and after each set of bag samples, whichever is more frequent.
7.4 Bag Leak Checks. While performance of this section is required
subsequent to bag use, it is also advised that it be performed prior to
bag use. After each use, make sure a bag did not develop leaks as
follows: to leak check, connect a water manometer and pressurize the
57
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in Figure 2. Evacuate a 50-liter Tedlar or aluminized Mylar bag that
has passed a leak check (described in Section 7.4) and meter in about
50 liters of nitrogen. Measure the barometric pressure, the relative
pressure at the dry gas meter, and the temperature at the dry gas meter.
While the bag is filling use the 10 yl syringe to inject 10 yl of 99 +
percent benzene through the septum on top of the impinger. This gives
a concentration of approximately 50 ppm of benzene. In a like manner,
use the other syringe to prepare dilutions having approximately 10 and
5 ppm benzene concentrations. To calculate the specific concentrations,
refer to section 8.1. These gas mixture standards may be used for
four days from the date of preparation, after which time preparation of
pew gas mixtures is required. (Caution: Contamination may be a
problem when a bag is reused if the new gas mixture standard is a lower
concentration than the previous gas mixture standard.)
7.2 Determination of Benzene Retention Time. This section can be
performed simultaneously with section 7.3. Establish chromatograph
,conditions identical with those in section 6.3, above. Determine proper
attenuator position. Flush the sampling loop with zero helium or
nitrogen and activate the sample valve. Record the injection time, the
sample loop temperature, the column temperature, the carrier gas flow
rate, the chart speed and the attenuator setting. Record peaks and
detector responses that occur in the absence of benzene. Maintain con-
ditions, with the equipment plumbing arranged identially to section 6.3,
and flush the sample loop for 30 seconds at the rate of 100 ml/min with
One of the benzene calibration mixtures and activate the sample valve.
58
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bag to 5-10 cm H20 (2-4 in. HgO). Allow to stand for 10 minutes. Any
displacement in the water manometer indicates a leak. Also, check the
rigid container for leaks in this manner. (Note: an alternative leak
check method is to pressurize the bag to 5-10 cm I-LO or 2-4 in. HJD and
allow to stand overnight. A deflated bag indicates a leak.) For each
sample bag in its rigid container, place a rotameter in line between
the bag and the pump inlet. Evacuate the bag. Failure of the rotameter
to register zero flow when the bag appears to be empty indicates a leak.
8. Calculations
8.1 Optional Benzene Standards Concentrations. Calculate each
benzene standard concentration prepared in accordance with section 7.1
as follows:
X(
Y
i
•0707 __> 10 yg ug .
•8/8/ mg' mg 78.
c.
v 10° yl
Y 1
X (270.6)
p
293 in
Tm 76°
mole
1 1 yg
293
Tm
m
24.055 yl inG
yg . mole
p
m
760
Equation 1
where:
C = The benzene standard concentration.
c
X = The number of yl of benzene injected.
Y = The dry gas meter reading in liters.
P = The absolute pressure of the dry gas meter, mm Hg.
m f
T = The absolute temperature of the dry gas meter, °A.
.8787 = The density of benzene at 293°A.
59
-------
78.11 = The molecular weight of benzene.
24.055 = Ideal gas at 293°A, 760 mm Hg.
10 = Conversion factor, ppm.
8.2 Benzene Sample Concentrations. From the calibration curve
described in section 7.3, above, select the value of C that corresponds
to A . Calculate C as follows:
c s
where: .
B .. = The water vapor content of the bag sample, as analyzed.
C = The concentration of benzene in the sample in ppm.
C = The concentration of benzene indicated by the gas chromatograph,
in ppm.
P = The reference pressure, the laboratory pressure recorded during
calibration, mm Hg.
Tj = The sample loop temperature on the absolute scale at the time
*• I
of analysis, °A.
P. = The laboratory pressure at time of analysis, mm Hg.
T = The reference temperature, the sample loop temperature recorded
during calibration, °A.
60
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APPENDIX E
LAAPCD TOTAL ORGANIC ACIDS METHOD
61
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Collection and Analysis of Gaseous Constituents
5.4.2 ORGANIC ACIDS
5.4.2.1 METHOD SUMMARY
The only collection method used by the
APCD for organic acids is continuous sampling
with an impinger absorption train. The proce-
dure entails the collection of the sample by
bubbling the gases through dilute caustic fol-
lowed by acidification and ether extraction of
the free organic acids. A liquid-liquid ex-
tractor is used to provide multiple contact of
ether and aqueous media. The organic acids in
ether are subsequently titrated with a standard
base and reported as acetic acid. The lower
limit of the method is about 0.2 ppm in a 60
cubic foot sample.
Aliquot portions of the impinger solution
can also be analyzed for total oxides of sul-
fur (see Sect.5.4.7).
69
62
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Source Testing Manual
5.4.2.2 PREPARATION FOR SAMPLING
The collection train is assembled as shown
in Figure 5.1. The first two impingers each
contain exactly 100 ml of 5% sodium hydroxide
solution, while the third is operated dry to
catch any carry-over spray and to protect the
gns rater. An ice bath is used to cool the im-
pinRcrs. Glass, quartz-composition, or stain-
less steel sampling probes of any. convenient
size may be used. All equipment is tested for
proper operation and freedom from leaks.
5.4.2.3 SAMPLING
Any convenient sampling rate, not to exceed
1 cfm, may be used. Proportional sampling, as
described in Section 5.2.1, may be necessary
when there are wide fluctuations in both gas
flow rate and. composition.
The data recorded during sampling should
include:
a) Time (clock) of test and data re-
cordings
b) Gas meter reading (initial), cubic
feet
c) Gas meter vacuum, inches of mercury
below atmospheric
d) Gas meter temperature, degrees Fah-
renheit
e) Temperature of gas at exit of third
impinger, degrees Fahrenheit .
Headings may be taken at five- or ten-minute
intervals during a one-hour test, and the data
arc recorded as indicated on the upper tabular
portion of Figure 4.9. Sampling for particulate
matter usually accompanies this procedure; if
this is not the case, reference point velocity
head and temperature readings should be made,
as described in Section 3.3.2.
At the completion of sampling, the pump is
shut off and the train allowed to come to at-
mospheric pressure before disconnecting the
vacuum line. The final gas meter reading is
70 63
recorded. The impingers and associated tubing
are suitably sealed for transfer to the labor-
atory for processing. Condensate, if any, in
the probe and inlet tubing is allowed to flow
into the first impinger.
5.4.2.4 SAMPLE PROCESSING
The total volume of liquid contained in
the impingers is carefully measured. The dif-
ference from the initial volume is recorded as
the condensate volume.
The impingers and associated tubing are
carefully rinsed with small portions of dis-
tilled water, the liquid and washings being
kept in a beaker or flask. If aliquots are to
be taken for analysis, the combined liquid and
washings are made up to an exact volume. Ali-
quots can be taken if the organic acids exceed
50 ppm by volume.
5.4.2.5 ANALYTICAL PROCEDURE
The reagents needed for the analysis are
concentrated sulfuric acid, reagent-grade ethyl
ether, and 0.1 N sodium hydroxide solution.
The 0.1 N sodium hydroxide solution should be
prepared and stored in a manner to avoid con-
tamination by atmospheric carbon dioxide. The
solution is standardized by titration using
potassium biphthalate (primary-standard grade)
and phenolphthalein indicator.
The liquid-liquid extractor (ItemNo. 92232,
Corning Glass Works, Corning, New York, or
equivalent) and water heating bath are shown
disassembled in Figure 5.5. The procedure for
each sample is as follows:
An 80-100 ml aliquot of the solution is
transferred to a 500-ml three-neck glass flask
equipped with a reflux condenser, separatory
funnel, and gas inlet tube. The latter should
project below the level of the liquid in the
flask. Four drops of methyl red indicator are
addod and the sample is acidified by addition
-------
Collection and Analysis of Gaseous Constituents
FIGURE 5.5. fguipnent u»erf /or extraction
of organic acids. Equipment shown is (1) jtea«
bath; (2) round 6ottoo flask; (3) extractor;
(4) inner coHector tube; (5) condenser.
of concentrated sulfuric acid from the sepa-
ratory funnel. During acidification, the sample
is agitated by intermittent bubbling of nitrogen
into the flask. After acidification, nitrogen
is bubbled through the sample until sulfur
dioxide ceases to evolve from the condenser
(determined by holding wet litmus test paper
strips at the top of the condenser). The sample
is now heated just to the boiling point to
ensure complete removal of SC^. The sample is
allowed to cool and the condenser is rinsed
'with water into the flask. The sample is trans-
ferred to a volumetric flask and diluted to a
suitable exact volume. Fifty ml aliquots are
transferred to 150—ml beakers and adjusted to
pH 2 (pH paper) with 30% sodium hydroxide so-
lution. A blank containing the same amount of
original sodium hydroxide as the aliquots is
adjusted to pH 2 with concentrated sulfuric
acid and is analyzed with the aliquot samples.
Transfer the sample and blank mixtures to
separate 500-ml liquid-liquid extractors. A
long-stemmed funnel is useful for making the
transfers. The final aqueous levels should be
3 or 4 inches below the side arms. Carefully
insert the inner collector tubes, and attach
the condensers and 500-ml round bottom flasks.
Slowly add ether through the condensers, allow-
ing it to rise in the extractors. Continue
adding ether until about 200 ml has overflowed
into the flasks. Heat the flasks to steady
boiling on water baths or with Glass-Col heat-
ing mantles, and allow the extractions to pro-
ceed for 8 hours.
After the flasks have cooled, tilt the ex-
tractors to allow as much as possible of the
ether to decant over into the flasks without
removing any aqueous material. Transfer the
ether extracts to separatory funnels and remove
any traces of aqueous material that may be
present. Add about 40 ml of water and 3 drops
of phenolphthalein indicator to each of the
ether solutions in the separatory funnels.
Titrate the mixtures in the funnels with stand-
ard 0.1 N sodium hydroxide to the phenolphtha-
lein end point. As the end point is approached,
stopper the separatory funnels and shake with
each small titration increment until a pink
color persists.
5.4.2.6 CALCULATIONS
The sequence of calculations, using the
data obtained during sampling, processing, and
analysis, is as follows:
a} Volume of stack gas sampled
6) Organic acid concentration
c) Emission rate of organic acids
d) Water vapor content of stack gas
The APCD forms shown in Figures 4.9 and 4.13
are convenient for many of the calculations to
be described.
5.4.2.5.1 Sample Volume
The volume of stack gas sampled is calcu-
lated in the same manner as described for ammo-
nia (Sect.5.4.1.6.1). It may be noted that a
slight error occurs in the sample volume cal-
culation when stack gases containing moderate
amounts of carbon dioxide are sampled with ab-
sorption trains containing sodium hydroxide
64
71
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Source Testing Manual
solution. The alkali will react with the car-
bon dioxide, forming water, sodium carbonate,
and possibly some bicarbonate. The pH of the
resulting solution is still high enough, how-
ever, for efficient absorption of oxides of
sulfur, organic acids, or fluorides. As a re-:
suit of this reaction, the measured condensate,
volume will be high due to production of water,
and the metered gas volume will be low due to
loss of a small volume of carbon dioxide from
the gas sample. These two small errors will
tend to cancel each other for calculation of
total sample volume.
5.0.2.6.2. Concentration
The weight of organic acids (expressed as
acetic acid) collected by the sampling train
is given by
W^ • 0.0601fn(vg - vb) , (5.7)
where,
WQ^ a weight of organic acids, grams
f a aliquot factor: the ratio of total
solution volume to aliquot volume
n = exact normality of 0.1 N sodium hy-
droxide
vs = volume of 0.1 N sodium hydroxide used
for the sample titration, milliliters
vjj a volume of 0.1 N sodium hydroxide used
for the blank titration, milliliters
The concentration of organic acids in the gas
sample is given by the two relations,
(5.8)
and
where,
15.53
13, 900
(5.9)
Q>\ = concentration of organic: acids (as
acetic acid), grains per standard
foot
CQ\ =concentration of organic acids, parts
per million by volume
Vj a volume of stack gas sampled, from
Equation 4.9, standard cubic feet
Although weight-volume concentrations (Fq. 5.8)
require that some particular acid such as ace-
tic be used as a basis, volume-volume concen-
trations (Eq. 5.9) will be the same for any
monocarboxylic acid.
5.4.2.6*.3 Emission Rate
The emission rate of organic acids at the
sampling station location is given by either
of the two relations,
= 0.008570^0 , (5.10)
9.52 x lO-Q , (5.11)
or
where,
MQ^ m emission rate of organic acids,
pounds per hour
£QJ{ a concentration, from Equation 5.8,
grains per standard cubic foot
CQ\ " concentration, from Equation 5.9,
parts per million by volume
Q « stack gas flow rate, from Equation
3.12, standard cubic feet per minute
5.4.2.6.4 Moisture Content
The water vapor content of the stack gases
is calculated by the procedure described in
Section 4.4.1.8.3. The calculation is made only
for comparison with the results from the par-
ticulate train processing. The difference is
due to errors in condensate volume and water
vapor volume calculations, caused by chemical
reactions during absorption and the lowered
vapor pressure (relative to pure water) of the
absorbent solution. Both effects mentioned will
produce small positive errors in calculation
of water vapor content.
72
65
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APPENDIX F
LAAPCD ALDEHYDES AND FORMALDEHYDE METHODS
66
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Source Testing Manual
5.4.3 ALDEHYDES
5.4.3.1 METHOD SUMMARY
In practically all tests, samples for
aldehyde analysis are collected in evacuated
flasks, using grab sampling techniques (Sect.
5.3.2). In rare instances, impinger absorption
trains have been used, but this collection
method is more applicable to the low aldehyde
67
72
-------
Collection and Analysis of Gaseous Constituents
concentrations experienced in atmospheric
monitoring.
In either case, aldehydes in the sample
react with a solution of sodium bisulfite to
form addition compounds. The excess bisulfite
ion is destroyed with iodine solution. By ad-
justing the pH of the solution, the addition
compounds are decomposed, freeing bisulfite
ion equivalent to the aldehydes present in the
sample. The liberated bisulfite ion is then
titrated with standard iodine. Methyl ketones,
i£ present in the sample, will be included in
the results. The lower limit of the method,
using 2-liter gas samples, is about 1 ppm.
Since the collection methods are iden- .
tical, aliquot portions of the solutions can
be analyzed for formaldehyde alone (Sect.
5.4.4).
5.4.3.2 PREPARATION FOR SAMPLING
Two-liter round bottom flasks, as shown in
Figure 5.2, are used for grab sampling. Ten ml
of 1% sodium bisulfite solution (Igper 100 ml
solution) are added to each flask. The flask
is then evacuated to the vapor pressure of the
solution, the screw clamp closed, and the solid
glass plug inserted into the open end of the
tubing until ready for sampling.
For continuous sampling by impingers, the
collection train is prepared as described for
ammonia or organic acids, adding exactly 100
ml of 1% sodium bisulfite solution to each of
the first two impingers.
'5.4.3.3 SAMPLING
The inlet tube of the 2-liter flask is
connected to one leg of a glass tee or three-
way stopcock attached to the sampling line.
An aspirator bulb, connected to the other leg
of the tee, is used for flushing the sample
probe and tubing with stack gas just prior to
sampling, as illustrated in Figure 5.6. The
FIGURE 5.6. Grab soup ling of a gas stream.
screw clamp is opened to admit gas to the
evacuated flask. When the flow of gas has
ceased, the screw clamp is closed and the
glass plug reinserted into the short rubber
tube to the flask. The flow of gas may con-
tinue for many minutes when the gases are
almost 100 per cent steam, thus requiring the
flask to be cooled during this process. Such
a situation may be encountered, for example,
when testing rendering cookers. The proced-
ure in Section 5.5.3 should then be followed
for calculations. In order to obtain an av-
erage value, four grab samples are usually
taken during an hour test.
When absorption impinger trains are used,
the sampling procedure is the same as described
for organic acids. The sampling rate should
not exceed 0.3 cfm.
5.4.3.4 SAMPLE PROCESSING
The sealed collection flasks are shaken
for 15 minutes on a mechanical shaker, with
frequent rotation to provide a thorough scrub-
bing action. The temperature and absolute gas
pressure in each flask are recorded after the
gases have reached ambient temperature. The
contents of each sample flask are then rinsed
68
73
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Source Testing Manual
into conical flasks. A blank is prepared,
using the same amount of \% sodium bisulfite
solution used for each sampling flask.
The impinger train collection is processed
in a manner analogous to that described for
organic acids in Section 5.4.2.4. Unless the
aldehyde concentration is very low (below 0.1
ppm), aliquots may be taken for analysis.
5.4.3.5 ANALYTICAL PROCEDURE
The analytical procedure is identical for
samples collected either by grab or absorption
train sampling.
The reagents needed for the analysis are
0.05 N sodium thiosulfate solution, 0.005 N
iodine solution, approximately 0.1 N iodine
solution (made by disolving 12.7 g of iodine
in a solution of 25 g of potassium iodide in
50 ml of water, and diluting to one liter
with water), and a special buffer solution.
The sodium thiosulfate solution is standard-
ized with potassium dichromate (primary
-standard grade) according to standard iodo-
metric procedure. The 0.005 N iodine solu-
tion, prepared by dilution from the 0.1 N so-
lution, is standardized by titration with
the sodium thiosulfate solution using
starch indicator. The buffer solution is pre-
pared by dissolving 80 g of anhydrous sodium
carbonate in 500 ml of water, slowly adding 20
ml of glacial acetic acid, followed by dilution
toil. The pH of the solution is adjusted to
9.6 ± 0.1 with sodium carbonate or acetic acid,
as required, using a pH meter.
Two ml of 1% starch indicator solution are
added to each sample, and 0.1 N iodine is added
dropwise until a dark blue color is produced.
Care should be taken to ensure that all of the
sulfur dioxide resulting from the decomposi-
tion of bisulfite is removed since it may
cause the end point to fade. This can be con-
veniently accomplished by blowing a small jet
of air into the flask while swirling the con-
tents vigorously for several minutes. Each
solution is decolorized by dropwise addition
of 0.05 N sodium thiosulfate. The 0.005 N
iodine solution is added, to a faint blue end
point. The solutions are cooled thoroughly in
an ice bath, and 50 ml of chilled buffer are
added to each flask. The flasks are kept in
the ice bath for 10 to 15 minutes after the
buffer addition. The liberated bisulfite is
titrated with 0,005 N iodine solution to the
same faint blue end point present before addi-
tion of the buffer. The sample must remain
chilled in order to avoid a fading end point.
5.4.3.6 CALCULATIONS: IMPINGE.R TRAIN
SAMPLES
The sequence of calculations for aldehyde
samples collected by impinger trains is as
follows:
a) Volume of stack gas sampled
6) Aldehyde concentration
c) Emission rate of aldehydes
5.4.3.6.1 Sample Volume
The calculations for the volume of stack
gas sampled are made in the same manner as
described previously, in Section 5.4.1.6, for
ammonia.
5.4.3.6.2 Concentration
The weight of aldehydes, expressed as for-
maldehyde, collected by the impinger train is
given by the expression
where,
f
o.oisfn(vs - vb)
(5.12)
of aldehydes collected, grams
= aliquot factor: ratio of total sol-
ution volume to aliquot volume
= exact normality of the 0.005 N
iodine solution
69
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Collection and Analysis of Gaseous Constituents
vs B volume of 0.005 N iodine solution
used for sample titration following
the addition of the buffer solution,
milliliters
vjj = volume of 0.005 N iodine solution
used for blank titration.,milliliters
The concentration of aldehydes in the gas
sample is given by the two relations,
'AID
f
and
where ,
27,-800
W,
'AID
(5.13)
(5.14)
concentration of aldehydes (as for-
maldehyde), grains per standard
cubic foot
CALD = concentration of aldehydes, parts
per million by volume
VT = total sampled volume, from Equation
4.9, standard cubic feet
Unlike weight-volume concentration, volume-
volume concentrations will be the sane for any
aldehyde or methyl ketone having one carbonyl
group per molecule.
5.4.3.6.3 Emission Rate
The emission rate, or mass flow rate, of
aldehydes at the sampling station location is
given by either of the two relations,
M
IALD* 0.00357 c^o , (5.15)
or
MAID = 4.75 x
(5.16)
where,
emission rate of aldehydes, pounds
per hour
concentration, from Equation 5.13,
grains per standard cubic foot
CAII) * concentration, from Equation 5.14,
parts per million by volume
Q • stack gas flow rate, from Equation
3.12, standard cubic feet per minute
5.4.3.7 CALCULATIONS: GRAB SAMPLES
The sequence of calculations for aldehyde
samples collected with evacuated flasks is as
follows:
a) Volume of stack gas sampled, dry
basis
b) Aldehyde concentration, dry basis
c) Aldehyde concentration, stack condi-
tions
d) Emission rate of aldehydes
5.4.3.7.1 Sample Volume
The dry volume of stack gas sampled is
calculated as follows:
Vf 520
760 T,
vf
-------
Source Testing Manual
excess moisture in the stack gases, precipi-
tated upon cooling in the flask, is usually
negligible in comparison with the absorbent
solution. Thus, moisture calculations from
measurements of the condensate, as done for
impinger trains, are not made. An exception
does, however, occur when sampling steam (see
Sect. 5.5.3).
5.4.3.7.2 Concentration *
The aldehyde concentrations are calculated
and reported in two ways: (1) on a dry basis;
and (2) on a wet basis, or under actual stack
water vapor conditions.
The calculation of aldehyde concentration
on a dry basis uses the relation,
(c
v
11.85 x 103 n(vs -
where, ,
^cALD^d 3 concentration of aldehydes, dry
basis, parts per million by vol-
ume
n = exact normality of the 0.005 N
iodine solution
vg 3 volume of 0.005 N iodine solution
used for the sample titration
following the addition of the
buffer solution, milliliters
vjj = volume of 0.005 N iodine solution
used for the blank titration,
milliliters
Vdg = dry volume of gas sample, from
Equation 5.17, standard liters
In order to convert concentrations from
the dry basis to stack water vapor conditions
(sometimes called the wet basis), the following
relation is used:
ALD
(100 - W.V.)
100
(5.19)
where ,
CAJLD ** concentration of aldehydes, at
stack conditions, parts per mil-
lion by volume
^cALD^d a concen'-ra*'ion of aldehydes, dry
basis from Equation 5.18, parts
per million hy volume
W.V. " water vapor content of stack gas,
per cent by volume
It may be noted that this is identical to the
concentration defined by Equation 5.14.
The water vapor content of the stack gas
is usually determined from the data obtained
when sampling and processing the collection
train or trains for particulate matter. In
other instances, it may be determined with a
condensate sampling train, or by dry-wet bulb
thermometry, as described in Section 5.5.
The concentrations may be converted from
vo lume -volume to weight-volume units using the
conversion
where,
CA1D = 0-000554 CAU) , (5.20)
concentration of aldehydes, ex-
pressed as formaldehyde, grains per
standard cubic foot
5. ft. 3.7. 3 Emission Rate
The emission rate, or mass flow rate, of
aldehydes at the sampling station location is
given by either of the two relations,
MAID* o.ooss?
(5.21)
or
MALD a 4<7S x 1(r6 CA1DQ ' (5'22)
where,
M^jj) a emission rate of aldehydes, as for-
maldehyde, pounds per hour
*-ALD = Concentrati°n> from Equation 5.20,
grains per standard cubic foot
76
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Collection and Analysis of Gaseous Constituents
CALO = concentration, from Equation 5.19,
parts per million by volume
Q " stack gas flow rate, from'Equation
3.12, standard cubic feet per minute
5.4.4 FORMALDEHYDE
5.4.4.1 METHOD SUMMARY
The methods of sample collection and pro-
cessing prior to analysis are identical to
those described for aldehydes. The samples are
collected in a dilute solution of sodium bisul-
fite. Any aldehydes present form the bisulfite
addition compounds. An aliquot of the resultant
solution is then treated with chromotropic
acid in strong sulfuric acid. Formaldehyde
forms a unique colored compound, the exact na-
ture of which is unknown but which appears to
be of a quinoidal type. The intensity of the
colored compound is then determined in a color-
imeter and the corresponding concentration of
formaldehyde read from a calibration curve.
The lower limit of the method, using 2-liter
gas samples, is about 1 ppm.
Two-liter round bottom flasks, prepared in
the same manner as described for aldehydes,
are used for sampling. Sampling and processing
of the flasks and collected samples also are
the same as described for aldehydes, except
that the solutions from each flask are meas-
ured to an exact volume, which should be as
small as possible.
5.4.4.2 PREPARATION OF REAGENTS
The special reagents needed for the analy-
sis are 0.05 N sodium thiosulfate solution,
approximately 0.1 N iodine solution, 0.005 N
iodine solution, buffer solution, standard
formaldehyde solution, 76% sulfuric acid solu-
tion, and chromotropic acid reagent.
The sodium thiosulfate, iodine, and buffer
solutions are prepared and standardized as
described for aldehydes; the other solutions
are prepared and standardized as follows:
Standard formaldehyde solution: Dilute 3 ml of
formalin (approximately 37%) to 1 1 in a volu-
metric flask. To standardize, pipet 1 ml of
the solution into a 250-ml Erlenmeyer flask,
and 1 ml of water into another flask as a
blank. Add 30 ml of 1% sodium bisulfite and 2
ml of 1% starch to each flask. Add 0.1 N iodine
dropwise to each flask until a dark blue color
results. Decolorize each flask with 0.05 N
sodium thiosulfate and then return to a faint
blue with 0.005 N iodine. Chill each flask in
an ice bath and add 50 ml of chilled buffer.
After addition of the buffer, allow to stand
in the ice bath for 10 to 15 minutes, then
titrate the liberated bisulfite in each flask
to the same faint blue end point with 0.005 N
iodine. Subtract the volume of 0.005 N iodine
used for the blank determination from the vol-
ume used for the sample determination. The
strength of the standard in micrograms per
milliliter is 1.5 x lO'* vn, where v is the
volume, in milliliters, of 0.005 N iod'.ne used
for titration following the addition of buffer,
less blank; and n is the exact normality of
the 0.005 N iodine.
Dilute 1 ml of this standard formaldehyde
solution to 1 1. The diluted solution contains
approximately 1.2 /^g of formaldehyde per ml.
76% sulfuric acid: Slowly add 725 ml of
concentrated sulfuric acid to 350 ml of water.
It is advisable to place the container in which
the dilution is to be made in a water bath to
absorb some of the heat generated.
Chromotropic acid reagent: Weigh 0.875 g
of 4,5-dihydroxy-2,7-naphthalenedisulfonic
acid, disodium salt (Eastman No. P230 or equiv-
alent) into a 100-ml beaker and add 4.25 ml of
water. Rapidly add 45.75 ml of 76% sulfuric
acid and stir to dissolve. Prepare fresh for
72
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Source Testing Manual
each Hay's analyses because this reagent de-
composes on standing. The final mixture con-
tains approximately 71% su If uric acid by weight.
Prepare a calibration curve for each new
bottle of chromotropic acid as follows: Trans-
fer 50 ml of 76/o sulfuric acid, by means of a
graduate, to each of a series of six 150-ml
beakers. Warm the solutions in a water bath to
60 i 2 C. Add 2 ml of chromotropic acid reagent
to each beaker. Pipet 1 ml of the 1.2 A*g per
ml standard formaldehyde solution and 4 ml of
water into the first beaker, 2 ml of the 1.2 /ug
per ml standard and 3 ml of water into the
second, 3 ml of the 1.2 £ig per ml standard and
2 ml of water into the third, 4 ml of the 1.2
Mg per ml standard and 1 ml of water into the
fourth, 5 ml of the 1.2 p-g per ml standard
into the fifth. The beakers will then contain
approximately 1.2, 2.4, 3.6, 4.8, and 6.0 jug
of formaldehyde per 5-ml aliquot, respectively.
Run a blank by adding 5 ml of water to the
sixth beaker containing chromotropic acid.
Stir the solutions frequently and maintain at
the specified temperature for 20 minutes. The
color reaction is, in part, dependent upon the
time in the bath and, to a lesser extent, upon
the time required !>efore making the colorimeter
reading. Hence, the sequence of events is crit-
ical. Likewise the solution temperature must
be closely controlled. At the end of 20 minutes
in the water bath, inmerse the beakers in ice
water. This procedure impedes the color devel-
opnent somewhat. Rapidly transfer to the col-
orimeter cell for reading. Measure the light
absorption of the solutions in the photoelec-
tric colorimeter (a Klett-Summerson industrial
colorimeter, No. 54, or equivalent) with a 500-
to 560-mit green filter and a 20 mm light path.
Use the blank solution for zeroing the color-
imeter. Prepare a calibration curve by plot-
ting the colorimeter readings against micro-
grams of formaldehyde contained in each solu-
tion.
5.4.4.3 ANALYTICAL PROCEDURES
Pour 50 ml of 76% sulfuric acid into each
of two 150-ml beakers. Warm the solutions in a
water bath to 60 ± 2 C. Add 2 ml of chromo-
tropic acid reagent to each. Transfer a 5-ml
aliquot of the sample by pipet to one beaker
and 5 ml of water to the other for a blank
determination. Stir the solutions frequently
and maintain at the specified temperature for
20 minutes. At the end of 20 minutes, remove
the beakers from the water bath and immerse
them in ice water. Rapidly transfer to the
colorimeter cells for reading. Measure the
light absorption of the solutions in the photo-
electric colorimeter with a 500- to 560-n\u
green filter and a 20-mm light path. Use the
blank for zeroing the colorimeter. Read the
weight of formaldehyde in micrograms from the
previously prepared calibration curve.
5.4.4.4 CALCULATIONS
The sequence of calculations for formal-
dehyde samples collected with evacuated flasks
is as follows:
a) Volume of stack gas sampled, dry
basis
b) Formaldehyde concentration, dry
basis
c) Formaldehyde concentration, stack
conditions
d) Emission rate of formaldehyde
The dry volume of stack gas sampled is
calculated using Equation 5.17.
The formaldehyde concentration is calcula-
ted on a dry basis by the relationship,
wFAf
(cFA)d =• 0.790-7;
(5.23)
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Collection and Analysis of Gaseous Constituents
where,
(c,,.). = formaldehyde concentration, dry
FA d
basis, parts per million by volume
%A = wei§ht of formaldehyde found in
5-ml aliquot of collection solu-
tion, micrograms
f = aliquot factor: ratio of total
collection solution volume to 5-ml
aliquot
Vj = dry volume of gas sample, from
Equation 5.17, standard liters
The conversion of formaldehyde concentra-
tion to stack moisture conditions is made using
Equation 5.19 and 5.20, previously given for
aldehydes. The conversion factors are identi-
cal, since total aldehydes are expressed as
formaldehyde.
The emission rate of formaldehyde,as for
aldehydes, is calculated by either Equation
5.21 or 5.22.
74 79
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